Plastic substrate having multi-layer structure and method for preparing the same

ABSTRACT

The present invention relates to a plastic substrate having a multi-layer structure and a method for preparing the same. The plastic substrate of the present invention comprises plastic films attached to each other, and a first buffering layer of an organic-inorganic hybrid, a layer of gas barrier, and a second buffering layer of an organic-inorganic hybrid which are stacked on both sides of the plastic films in an orderly manner, each layer forming a symmetrical arrangement centering around the plastic films. Because the plastic substrate of the present invention has a small coefficient of thermal expansion, excellent dimensional stability, and superior gas barrier properties, it can replace the brittle and heavy glass substrate in display devices. Also, it can be used for a variety of packaging or container materials in applications requiring superior gas barrier properties.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Continuation of application Ser. No. 11/882,114,filed Jul. 30, 2007, which is a Divisional of application Ser. No.11/049,939, filed Feb. 4, 2005, now U.S. Pat. No. 7,393,581, whichclaims priority of Korean Patent Application Nos. 10-2004-0007909 filedon Feb. 6, 2004 and 10-2005-0010375 filed on Feb. 4, 2005 in the KoreanIntellectual Property Office, which are hereby incorporated by referenceas if fully set forth herein

BACKGROUND OF THE INVENTION

(a) Field of the Invention

The present invention relates to a plastic substrate having amulti-layer structure with a small coefficient of thermal expansion,excellent dimensional stability, and superior gas barrier properties anda method for preparing the same.

(b) Description of the Related Art

Although glass plates used for display devices, picture frames,craftwork, containers, etc. are advantageous in that they have a smallcoefficient of linear expansion, superior gas barrier properties, hightransparency, good surface flatness, excellent heat resistance andchemical resistance, etc., they tend to break easily and be heavybecause of their high density.

Recently, as liquid crystal displays, organic light emitting devices,and electronic paper are arousing a growing interest, research onreplacing the glass substrates used in such devices with plasticcounterparts is gaining momentum. The plastic substrate is advantageousover the glass plate in terms of weight and ease of design. Also,because it is impact-resistant, an economic advantage may be attainedfrom continuous manufacturing.

For a plastic substrate to be used in a display device, it should have aglass transition temperature high enough to endure the transistorprocessing temperature and the transparent electrode depositiontemperature, oxygen and water vapor barrier properties so as to preventaging of liquid crystals and organic light emitting materials, a smallcoefficient of thermal expansion and good dimensional stability so as toprevent deformation of the plate due to change of the processingtemperature, mechanical strength comparable to that of the conventionalglass plate, chemical resistance sufficient for enduring the etchingprocess, high transparency, low birefringence, good surface scratchresistance, etc.

However, because a single polymer composite film (polymer film orpolymer-inorganic material composite film) that satisfies all therequirements does not exist, several layers of functional coats areapplied on a polymer film to fulfill them. Typical coating layers are anorganic flattening layer for reducing surface defects and offeringflatness, an inorganic barrier layer for blocking gaseous materials suchas oxygen and water vapor, and an organic or organic-inorganic hardcoating layer for offering surface scratch resistance. The conventionalplastic substrates having a multi-layer structure are manufactured bycoating an inorganic gas barrier layer on a plastic film and coating ahard coating layer on the gas barrier layer. In such a multi-layerstructure, deformation of the plastic film or cracking or peeling of theinorganic layer may occur because of the difference of coefficients oflinear expansion of the plastic film and the gas barrier layer.Accordingly, design of an appropriate multi-layer structure capable ofminimizing stress at the interface of each layer and adhesion of eachcoating layer are very important.

Vitex Systems of the U.S. developed a substrate having a superior gasbarrier property by obtaining an organic-inorganic multi-layer structureof several layers by forming a thin monomer film on a plastic film,polymerizing the monomer by illuminating UV (solidified organic layer),and forming a thin inorganic layer thereon by sputtering. Although asubstrate having a superior gas barrier property can be obtained withthis method, the requirement of a low coefficient of linear expansion,which is needed for a display, has not been satisfied, and a solutionmethod for the problem has not yet been suggested.

U.S. Pat. No. 6,465,953 disclosed a method of dispersing getterparticles capable of reacting with oxygen and water vapor on a plasticfilm to use for an organic light emitting device which is sensitive tooxygen and water vapor. The getter particles should have a particle sizesmaller than the characteristic wavelength of the emitted light, andshould be dispersed uniformly so that the emitted light can transmit tothe substrate without being scattered. This method is intended tominimize inflow of oxygen and water vapor by coating a gas barrier layercomprising an inorganic material on a plastic film. However, it isdifficult to uniformly distribute nano particles having a particle sizeranging from 100 to 200 nm, and the plastic film should be thick enoughto comprise a lot of getter particles capable of reacting with oxygenand water vapor. Also, because the inorganic gas barrier layer isdirectly coated on the plastic film, the gas barrier layer tends tocrack or peel off with changes in temperature.

U.S. Pat. No. 6,322,860 disclosed a plastic substrate for electronicdisplay applications that was manufactured by coating a crosslinkablecoating composition (comprising a polymer selected from the groupconsisting of polyfunctional acrylate monomers or oligomers,alkoxysilanes, etc. and a mixture thereof) on one or both sides of apolyglutarimide sheet having a thickness of no more than 1 mm, which hasbeen prepared by extrusion, and photocuring or thermally curing it toform a crosslinked coating, and coating a gas barrier layer on thecrosslinked coating and then coating another crosslinked coating on thebarrier layer, if necessary. In specific cases, transmission rate ofoxygen and water vapor was small enough to be used for a liquid crystaldisplay. However, a small coefficient of thermal expansion and superiordimensional stability, which are required to replace the glasssubstrate, were not obtained.

U.S. Pat. No. 6,503,634 disclosed a multi-layer substrate manufacturedby coating an organic-inorganic hybrid (ORMOCER) and silicon oxide on aplastic film or between two sheets of plastic films. The resultant filmshowed an oxygen transmission rate of no more than 1/30 and a watervapor transmission rate of no more than 1/40, compared with those beforecoating. Although this film can be used in packaging because ofsignificantly reduced oxygen and water vapor transmission rate, therewas no mention about improvement in the coefficient of thermal expansionor dimensional stability.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a plastic substratehaving a multi-layer structure, which has a small coefficient of thermalexpansion, excellent dimensional stability, and superior gas barrierproperties, and thus is capable of replacing the brittle and heavy glassplate.

It is another object of the present invention to provide a method forpreparing a plastic substrate having a multi-layer structure which canbe used for a display device and a variety of packaging and containermaterials requiring superior gas barrier properties.

To attain the objects, the present invention provides a plasticsubstrate having a multi-layer structure, comprising:

plastic films attached to each other, and

a first buffering layer of an organic-inorganic hybrid, a layer of gasbarrier, and a second buffering layer of an organic-inorganic hybridwhich are stacked on both sides of the plastic films in an orderlymanner, each layer forming a symmetrical arrangement centering aroundthe plastic films.

The present invention also provides a method for preparing a plasticsubstrate having a multi-layer structure comprising the steps of:

a) forming a first organic-inorganic hybrid buffer layer on one side ofa plastic film by coating a buffer composition in the sol state thereonand curing it;

b) forming a gas barrier layer on the first organic-inorganic hybridlayer by coating an inorganic material thereon;

c) forming a second organic-inorganic hybrid buffer layer on the gasbarrier layer by coating the buffer composition of the step a) andcuring it to prepare a multi-layer film;

d) preparing another multi-layer film having the same structure as thatobtained in the step c); and

e) attaching the plastic film of the step c) and the step d), so thatthe sides with no multi-layer film contact each other.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the cross-section of the plastic substrate having amulti-layer structure according to the present invention.

FIG. 2 shows a process for preparing the plastic substrate having amulti-layer structure according to the present invention.

FIGS. 3 to 8 show the cross-section of the plastic substrate accordingto Comparative Examples 1 to 6.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereunder is given a detailed description of the present invention.

The present invention is characterized by a plastic substrate having asmall coefficient of linear expansion and superior dimensional stabilityand gas barrier properties, thereby being capable of replacing the glasssubstrate of a display device, etc., and a method for preparing thesame.

In the plastic substrate of the present invention, an organic-inorganichybrid buffer layer is positioned between plastic films and a gasbarrier layer and on the gas barrier layer to minimize a difference ofthe coefficient of thermal expansion of each layer and improve theadhesion thereof.

The plastic substrate of the present invention is characterized bysymmetrical attached structure comprising various layers. If any onelayer in the structure is not, the function of the substrate can not bemanifested. Thus, the plastic substrates of the present inventioncomprise essentially symmetrical various layers as follows.

Because the plastic substrate of the present invention has a symmetricalstructure, it is not bent or deformed as the temperature changes.

According to the present invention, a plastic substrate having good gasbarrier properties, a small coefficient of thermal expansion andexcellent dimensional stability can be prepared easily by simplyattaching two plastic films using inexpensive equipment.

The plastic substrate of the present invention will be described morefully hereinafter with reference to the accompanying drawings, in whichpreferred embodiments of the invention are shown.

The plastic substrate of the present invention has the structure shownin FIG. 1, and a process for preparing it is shown in FIG. 2.

The plastic substrate of the present invention has a multi-layerstructure of two plastic film layers, two gas barrier layers and fourorganic-inorganic hybrid buffer layers.

As seen in FIGS. 1 and 2, the plastic substrate 100 of the presentinvention comprises attached plastic films 110 a, 110 b, and firstorganic-inorganic hybrid buffer layers 115 a, 115 b, gas barrier layers120 a, 120 b, and second organic-inorganic hybrid buffer layers 125 a,125 b which are stacked on both sides of the plastic films in an orderlymanner, each layer forming a symmetrical arrangement centering aroundthe plastic films. In FIGS. 1 and 2, the plastic substrate 100 refers tothe combination of symmetric layers attached to the side of the plasticfilms of each of the multi-layer films 100 a, 100 b that are attached toeach other centered on an attaching layer 130.

The first organic-inorganic hybrid buffer layer reduces a difference inthe coefficients of thermal expansion of the plastic films and the gasbarrier layer. Also, an adhesion of the plastic films to the gas barrierlayer can be improved by adjusting compositions of the organic andinorganic constituents. In addition, it can increase adhesion to the gasbarrier layer and minimize surface defects by flattening the surface ofthe plastic films.

The gas barrier layer is a dense inorganic material layer having a smallcoefficient of linear expansion and that blocks such gasses as oxygenand water vapor.

The second organic-inorganic hybrid buffer layer prevents cracking ofthe gas barrier layer, as well as further improving gas barrierproperties by filling defects of the gas barrier layer. In addition, itcan lower electrical resistance through its superior flattening ability,when forming a transparent conducting film.

The first organic-inorganic hybrid buffer layer and the secondorganic-inorganic hybrid buffer layer have the effects by preparing frompartial hydrolysis of a buffer composition comprising the organic silaneand the metal alkoxide.

The plastic films used in the present invention may be selected from thegroup consisting of a homopolymer, a polymer blend, and a polymercomposite including organic or inorganic additives. When the plasticsubstrate of the present invention is used for a liquid crystal displaydevice, a polymer having good heat resistance should be used because themanufacturing processes of thin-film transistors and transparentelectrodes involves high temperature of 200° C. or above. Examples ofsuch polymers are polynorbornene, aromatic fullerene polyester,polyethersulfone, bisphenol A polysulfone, polyimide, etc. As researchon reducing the temperature of the substrate manufacturing process toabout 150° C. proceeds, it has become possible to use such polymer suchas polyethylene terephthalate, polyethylene naphthalene, polyarylate,polycarbonate, cyclic olefin copolymer, etc.

Also, a plastic film obtained by dispersing nano particles on a polymercan be used. A typical example of such a polymer composite material isthe polymer-clay nanocomposite, which is advantageous in improvingmechanical properties, heat resistance, gas barrier properties,dimensional stability, etc. because of the small particle size and largeaspect ratio of the clay. In order to improve the above properties, itis important to disperse the platelets with the clay removed in alayered structure uniformly on a polymer matrix, and the materialsatisfying these conditions is the polymer-clay nanocomposite. Examplesof the polymer-clay nanocomposite that can be used for the polymer-claycomposite are polystyrene, polymethacrylate, polyethylene terephthalate,polyethylene naphthalene, polyarylate, polycarbonate, cyclic olefincopolymer, polynorbornene, aromatic fullerene polyester,polyethersulfone, polyimide, epoxy resin, polyfunctional acrylate, etc.For the clay, laponite, montmorillonite, magadite, etc. may be used.

The plastic film in the plastic substrate of the present invention has afilm or sheet form having a thickness of 10 to 1,000 microns (μm). Theplastic films can be prepared by solution casting or film extrusion. Itis preferred to anneal the prepared polymer substrate for severalseconds to several minutes at a temperature near the glass transitiontemperature in order to minimize deformation by temperature change.After annealing, a primer may be coated on the surface of the plasticfilm or surface treatment using corona, oxygen, or carbon dioxideplasma, and UV-ozone or reactive gas ion beams, etc. may be performed inorder to improve coating characteristics or adhesion.

The plastic substrate of the present invention is prepared as follows. Abuffer composition in the sol state is coated on one side of plasticfilms and cured to form a first organic-inorganic hybrid buffer layer.Then, an inorganic material is deposition coated on the firstorganic-inorganic hybrid buffer layer to form a gas barrier layer. Next,another buffer composition is coated and cured to form a secondorganic-inorganic hybrid buffer layer. As a result, a multi-layer filmis obtained. Another multi-layer film is prepared by following the sameprocess. Then, the two multi-layer films are attached so that the sidesof the plastic films on which the multi-layer films are not formed areadjacent to each other.

The first organic-inorganic hybrid buffer layer can be obtained bypartly hydrolyzing a buffer composition to form a sol-state solution,coating it on the plastic films, and curing the substrate. The coatingmay be performed by spin coating, roll coating, bar coating, dipcoating, gravure coating, spray coating, etc. The curing may beperformed by thermal curing, UV curing, IR curing, high frequency heattreatment, etc. After curing, the organic-inorganic hybrid buffer layerhas a thickness of 0.5-20 microns (μm), preferably 2-10 μm, and morepreferably 1-5 μm.

The buffer composition for preparing the organic-inorganic hybrid bufferlayer comprises an organic silane and a metal alkoxide. If necessary, itmay further comprise an adequate additive, a solvent, and apolymerization catalyst.

The organic silane may be at least one selected from the groupconsisting of the compounds represented by Chemical Formula 1 below.When one kind of compound is used, the organic silane compound should becapable of crosslinking.

(R¹)_(m)—Si—X_((4-m))  (1)

where X, which may be identical or different, is hydrogen, halogen,C₁₋₁₂ alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl, or —N(R²)₂ (whereR² is H or C₁₋₁₂ alkyl);

R¹, which may be identical or different, is C₁₋₁₂ alkyl, alkenyl,alkynyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl,arylalkynyl, alkynylaryl, halogen, substituted amino, amide, aldehyde,keto, alkylcarbonyl, carboxy, mercapto, cyano, hydroxy, C₁₋₁₂ alkoxy,C₁₋₁₂ alkoxycarbonyl, sulfonate, phosphate, acryloxy, methacryloxy,epoxy, or vinyl;

oxygen or —NR² (where R² is H or C₁₋₁₂ alkyl) may be inserted betweenR.sup.1 and Si to give —(R¹)_(m)—O—Si—X_((4-m)) or(R¹)_(m)—NR²—Si—X_((4-m)); and

m is an integer of 1-3.

The organic silane may be selected from the group consisting ofmethyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane,phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane,diphenyldimethoxysilane, diphenyldiethoxysilane, phenyldimethoxysilane,phenyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane,phenylmethyldimethoxysilane, phenylmethyldiethoxysilane,trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane,triphenylethoxysilane, phenyldimethylmethoxysilane,phenyldimethylethoxysilane, diphenylmethylmethoxysilane,diphenylmethylethoxysilane, dimethylethoxysilane, dimethylethoxysilane,diphenylmethoxysilane, diphenylethoxysilane,3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,p-aminophenylsilane, allyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane,3-glycidoxypropyldiisopropylethoxysilane,(3-glycidoxypropyl)methyldiethoxysilane,3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane,3-mercaptopropyltriethoxysilane,3-methacryloxypropylmethyldiethoxysilane,3-methacryloxypropylmethyldimethoxysilane,3-methacryloxypropyltrimethoxysilane,n-phenylaminopropyltrimethoxysilane, vinylmethyldiethoxysilane,vinyltriethoxysilane, vinyltrimethoxysilane, and a mixture thereof.

The metal alkoxide may be at least one selected from the groupconsisting of compounds represented by Chemical Formula 2 below.

M-(R³)_(z)  (2)

where M is a metal selected from the group consisting of aluminum,zirconium, and titanium;

R³, which may be identical or different, is halogen, C₁₋₁₂ alkyl,alkoxy, acyloxy, or hydroxy; and

Z is an integer of 3 or 4.

The filler may be at least one material selected from the groupconsisting of metal, glass powder, diamond powder, silicon oxide(SiO_(x), where x is an integer of 2-4) and clay. Examples of the fillerare metal, glass powder, diamond powder, silicon oxide, clay (bentonite,smectite, kaolin, etc.), calcium phosphate, magnesium phosphate, bariumsulfate, aluminum fluoride, calcium silicate, magnesium silicate, bariumsilicate, barium carbonate, barium hydroxide, aluminum silicate, and amixture thereof.

The solvent may be any one commonly used for partial hydrolysis, andpreferably distillation water. The catalyst is also not particularlylimited, and is preferably used aluminum butoxide, and zirconiumpropoxide etc.

The amount of filler, the solvent and the catalyst is not particularlylimited because of adding according to a necessary.

In the buffer composition, an amount of the organic silane is preferablycomprised at 20-99.99 wt %, more preferably at 50-99 wt %, and mostpreferably at 70-99 wt %. The amount of the metal alkoxide may becomprised at 0.01-80 wt %, more preferably at less than 70 wt %, andmost preferably at less than 20 wt %.

In the present invention, a surface flatness of the firstorganic-inorganic hybrid buffer layer, Ra (average of roughness) is veryimportant. If the buffer layer does not have sufficient flatness,defects occur when deposition of the gas barrier layer occurs, and thegas barrier property eventually disappears. Therefore, the smaller theflatness value, the greater the barrier property is increased. The firstorganic-inorganic hybrid buffer layer preferably has a surface flatnessof about 1 nm, more preferably no more than 1 nm. The preferredembodiments of the invention may have a surface flatness (Ra value) of0.5-1.2.

When inorganic gas barrier layer 120 a, 120 b is formed on the resultantbuffer layer, adhesion of the inorganic material layer to theorganic-inorganic hybrid buffer layer and gas barrier properties areimproved. Also, because the inorganic material layer has a high modulusand a small coefficient of linear expansion, mechanical properties ofthe substrate can be improved.

Because the plastic film has transmission rate of oxygen and water vaporof the order of several tens to several thousands, the gas barrier layercan be prepared by deposition coating a dense, transparent inorganicmaterial, or a thin metal film having a thickness of several nanometerson a polymer film, physically or chemically, in order to block oxygenand water vapor. When a transparent inorganic oxide film is used, it isdifficult to block oxygen and water vapor efficiently if pin holes orcracks exist. Also, it is difficult to obtain a uniform thin metal filmhaving a thickness of several nanometers and to obtain visible lighttransparency exceeding 80%. The resultant gas barrier layer has athickness of 5-1,000 nm, preferably 20-500 nm, and more preferably50-200 nm.

The inorganic material may be a metal oxide or a metal nitride of leastone selected from the group consisting of SiO_(x) (where x is an integerof 1-4), SiO_(x)N_(Y) (where each of x and y is an integer of 1-3),Al₂O₃, and ITO. The deposition coating may be performed by sputtering,chemical deposition, ion plating, plasma chemical deposition, a sol-gelmethod, etc.

Second organic-inorganic hybrid buffer layer 125 a, 125 b formed on thegas barrier layer minimizes cracking of the barrier layer and offerschemical resistance and scratch resistance to the surface. It mayfurther contribute to improvement of gas barrier properties throughhydration of the hydroxyl groups of the inorganic material layer withthe hydroxyl groups of the buffer layer at the deformed portion in whichpin holes or cracks exist. The composition used for the secondorganic-inorganic hybrid buffer layer stacked on the gas barrier layersis identical to that used for the first organic-inorganic hybrid bufferlayer coated on the plastic film. However, the proportion of the organicsilane, the metal alkoxide, and the filler and the coating thickness maybe different.

Second organic-inorganic hybrid buffer layer 125 a, 125 b may be formedby coating a sol-state solution on a polymer film by spin coating, rollcoating, bar coating, dip coating, gravure coating, spray coating, etc.,and curing it by thermal curing, UV curing, IR curing, or high frequencyheat treatment, as for the first organic-inorganic hybrid buffer layer.After curing, the buffer layer has a thickness of 0.5-20 microns (μm),preferably 2-10 μm, and more preferably 1-5 μm.

In the present invention, the surface flatness of the secondorganic-inorganic buffer layer is also an important. The devices such asITO used in the LCD or OLED process is deposited on the secondorganic-inorganic buffer layer directly, and thus if the flatness is ahigh, the devices can not an essential the function due to theconcentration phenomenon of an electric current.

Current trend is that OLED as the next generation displays than LCDdemands more superior flatness. Thus, the second organic-inorganichybrid buffer layer preferably also has a surface flatness of about 1nm, more preferably no more than 1 nm. The preferred embodiments of theinvention may have a surface flatness (Ra) of 0.5˜1.2.

Each of the multi-layer plastic films may be attached using an acrylicadhesive or hot melt method, although it is not limited to them. When anadhesive is used, its content is not particularly limited, butpreferably, the thickness of the attaching layer is 0.1-10 microns (μm).

As mentioned above, the plastic substrate of the present invention has acoefficient of linear expansion that is very small (to a maximum of 6.5ppm/K), and the gas barrier property is superior because the water vaportransmission rate is less than 0.005 g/m²/day. Therefore, the plasticsubstrate of the present invention can be substituted for a glasssubstrate which is breakable and heavy that is currently used in displaydevices etc. of the related art. In addition, the plastic substrates ofthe present invention can be used as a material for which superior gasbarrier properties are demanded, in addition to the display devices.

Hereinafter, the present invention is described in more detail throughexamples. However, the following examples are only for the understandingof the present invention and the present invention is not limited to orby them.

EXAMPLES Example 1

A PET (polyethylene terephthalate, SH38, SK of Korea) film having athickness of 100 microns, which had been acryl primer coated on bothsides by biaxial drawing extrusion, was heat treated in a convectionoven of 150° C. for 1 minute to remove residual stress. The resultantfilm was used for plastic films.

In order to form a first organic-inorganic hybrid buffer layer, 80.0parts by weight of distilled water was added to a mixture comprising32.5 parts by weight of tetraethoxysilane, 64.0 parts by weight of3-glycidoxypropyltrimethoxysilane, 0.5 parts by weight ofaminopropyltrimethoxysilane, 2.0 parts by weight of aluminum butoxideand 1.0 part by weight of zirconium propoxide. Partial hydrolysis wasperformed at 25° C. for 24 hours to prepare a buffer composition in thesol state. The buffer composition was bar coated on one side of the PETfilm. Gelation was performed in a convection oven of 125° C. for 1 hourafter drying the film at 50° C. for 3 minutes to remove the solvent.After gelation, thickness of the organic-inorganic hybrid buffer layerwas measured using an alpha stepper. The thickness was 3 microns. A thinsilicon oxide (SiO_(x), x=integer of 1-4) film was deposited on thebuffer layer by impregnating 50 sccm of Ar gas using a DC/RF magnetronsputter of A-tech System and performing deposition at a pressure of 5mtorr for 10 minutes with an RF (13.56 MHz) power of 1,000 watts. Whenthe silicon oxide film was observed by SEM, it had a thickness of 100nm. The above buffer composition was bar coated on the silicon oxidefilm. Gelation was performed in a convection oven of 125° C. for 1 hourafter drying the film at 50° C. for 3 minutes to remove the solvent toform a second organic-inorganic hybrid buffer layer. As a result, amulti-layer film was obtained (100 b in FIGS. 1 and 2). After gelation,thickness of the organic-inorganic hybrid buffer layer was measuredusing an alpha stepper. The thickness was 3 microns.

Surface roughness of the second organic-inorganic hybrid buffer layermeasured by AFM room-temperature tapping mode was no more than 0.4 nm atan area of 50 microns.times.50 microns.

Another multi-layer film (100 a in FIGS. 1 and 2) was prepared followingthe same process.

An adhesive composition comprising a polyfunctional acrylate oligomer asa main constituent was bar coated on the non-coated PET surface of themulti-layer film (100 b). It was attached with the multi-layer film (100b). UV was illuminated for 6 minutes using DYMAX 2000-EC to cure theadhesive composition. Resultantly, a plastic substrate having astructure of 100 in FIG. 1 was obtained.

Major properties required for a display device, such as transparency,haziness, oxygen transmission rate, water vapor transmission rate,coefficient of thermal expansion, and pencil scratch hardness of theplastic substrate were measured. The results are shown in Table 1 below.Measurements were performed as follows for all Examples and ComparativeExamples.

1) Transparency: Measured in the visible region of 380-780 nm using a UVspectrometer of Varian according to ASTM D1003.

2) Haze: Measured using a haze meter TC-H3DPK of Tokyo Denshokuaccording to ASTM D1003.

3) Oxygen transmission rate: Measured at room temperature and RH 0%using OX-TRAN 2/20 of Mocon according to ASTM D 3985.

4) Water vapor transmission rate: Measured at room temperature and RH100% for 48 hours using PERMATRAN-W-3/33 according to ASTM F 1249.

5) Coefficient of thermal expansion: Measured using a thermo-mechanicalanalyzer (TMA) under a stress of 5 gf while increasing temperature by10° C. according to ASTM D696.

6) Pencil scratch hardness: Measured under a load of 200 g according toASTM D3363.

All the properties were measured at least five times and then averaged.

For reference, the PET film used in Example 1 had an oxygen transmissionrate of 25 cc/m²/day/atm, a water vapor transmission rate of 4.5g/m²/day, and a coefficient of thermal expansion of 22.4 ppm/K.

TABLE 1 Water vapor Coefficient Oxygen transmission of thermal Penciltransmission rate^(a)) rate^(b)) expansion Transparency Haze scratch(cc/m²/day/atm) (g/m²/day/atm) (ppm/K) (400 nm) (%) hardness Example 1<0.05 <0.005 3.4 >85% <0.3 >3H Immeasurable Immeasurable ^(a))Measurablelimit: 0.05 cc/m²/day/atm ^(b))Measurable limit: 0.005 g/m²/day

When the plastic substrate prepared in Example 1 was placed on a flatsurface, no bends were observed. Thus, as shown in the table 1, theplastic substrate had superior gas barrier properties, a smallcoefficient of thermal expansion, and good dimensional stability.

Example 2

A kapton polyimide film of DuPont having a thickness of 50 microns wassurface-treated with corona (A-Sung). A sol-state buffer composition thesame as that used in Example 1 was bar coated on the film. Gelation wasperformed in a convection oven of 200° C. for 30 minutes after dryingthe film at 50° C. for 3 minutes to remove the solvent. After gelation,thickness of the buffer coating layer was measured using an alphastepper. The thickness was 2 microns. A thin silicon oxide film wasdeposited on the buffer coating layer in the same manner of Example 1.The above buffer composition was bar coated on the silicon oxide film.Gelation was performed in a convection oven of 200° C. for 30 minutesafter drying the film at 50° C. for 3 minutes to remove the solvent toform a second buffer coating layer. Thickness of the second buffercoating layer measured with an alpha stepper was 2 microns. Theresultant multi-layer film was attached with another multi-layer film,which was prepared in the same manner as in Example 1 to prepare aplastic substrate having the structure of 100 in FIG. 1.

Properties of the plastic substrate were measured as in Example 1. Theresults are given in Table 2 below.

TABLE 2 Water vapor Coefficient Oxygen transmission of thermal Penciltransmission rate rate expansion Transparency Haze scratch(cc/m²/day/atm) (g/m²/day/atm) (ppm/K) (400 nm) (%) hardness Example 2<0.05 <0.005 6.5 >85% <0.3 >3H

Example 3

The material used 40.0 parts by weight of tetraethoxysilane, 56.5 partsby weight of 3-glycidoxypropyltrimethoxysilane, 0.5 parts by weight ofaminopropyltrimethoxysilane, 2.0 parts by weight of aluminum butoxide,and 1.0 parts by weight of zirconium propoxide to form the firstorganic-inorganic hybrid buffer layer on the plastic film(PET) in thesame manner of Example 1. To buffer composition of sol state wasprepared by adding 60.0 parts by weight of distillation water in thematerials mixture, and then by the partial hydrolysis reaction at 25° C.for 24 hours. A sol-state buffer composition the same as that used inExample 1 was bar coated on one side of the PET film. Gelation wasperformed in a convection oven of 125° C. for 1 hour after drying thefilm at 50° C. for 3 minutes to remove the solvent. After gelation,thickness of the buffer coating layer was measured using an alphastepper. The thickness was 2 microns. A thin silicon oxide layer wasdeposited on the buffer coating layer in the same manner of Example 1.The above buffer composition was bar coated on the silicon oxide film.Gelation was performed in a convection oven of 125° C. for 1 hour afterdrying the film at 50° C. for 3 minutes to remove the solvent to form asecond buffer coating layer. Thickness of the second buffer coatinglayer measured with an alpha stepper was 2 microns. The resultantmulti-layer film was attached with another multi-layer film, which wasprepared in the same manner as in Example 1 to prepare a plasticsubstrate having the structure of 100 in FIG. 1.

Properties of the plastic substrate were measured as in Example 1. Theresults are given in Table 2 below.

TABLE 3 Water vapor Coefficient Oxygen transmission of thermal Penciltransmission rate rate expansion Transparency Haze scratch(cc/m²/day/atm) (g/m²/day/atm) (ppm/K) (400 nm) (%) hardness Example 3<0.05 <0.005 4.0 >85% <0.3 >3H

Comparative Example 1

A plastic substrate shown in FIG. 3 was prepared by attaching with twomulti-layer films, which was prepared in the same manner of Example 1,except for coating an organic-inorganic hybrid buffer layer only on thegas barrier layer without coating it between the PET film and thesilicon oxide gas barrier layer.

The buffer layer coated on the silicon oxide gas barrier layer wasprepared in the same manner of Example 1. Properties of the resultantplastic substrate were measured. The results are given in Table 4 below.

TABLE 4 Oxygen Water vapor Coefficient of transmission rate transmissionrate thermal expansion Transparency Haze (cc/m²/day/atm) (g/m²/day/atm)(ppm/K) (400 nm) (%) Comparative <0.05 <0.005 22.0 >85% <0.3 Example 1

As seen in Table 4, the plastic substrate prepared in ComparativeExample 1 showed oxygen and water vapor transmission rate exceeding themeasuring limit. It also showed a large coefficient of linear expansion,which is comparable to 22.4, or the coefficient of thermal expansion ofthe PET substrate itself because of comprising only one buffer layer.

Comparative Example 2

A plastic substrate shown in FIG. 4 was prepared by attaching with twomulti-layer films, which was prepared in the same manner of Example 1,except for coating the first organic-inorganic hybrid buffer layer onPET film and then by depositing the silicon oxide gas barrier layerwithout coating it the second organic-inorganic hybrid buffer layer onthe barrier layer.

The buffer layer coated on the plastic film was prepared in the samemanner of Example 1. Properties of the resultant plastic substrate weremeasured. The results are given in Table 5 below.

TABLE 5 Oxygen Water vapor Coefficient of transmission rate transmissionrate thermal expansion Transparency Haze (cc/m²/day/atm) (g/m²/day/atm)(ppm/K) (400 nm) (%) Comparative <0.05 <0.005 22.2 >85% <0.3 Example 2

As seen in Table 5, the plastic substrate prepared in ComparativeExample 2 showed oxygen and water vapor transmission rate exceeding themeasuring limit. It also showed a large coefficient of thermalexpansion, which is comparable to 22.4, or the coefficient of thermalexpansion of the PET substrate itself because of comprising only onebuffer layer.

Comparative Example 3

A plastic substrate shown in FIG. 5 was prepared by attaching with twomulti-layer films, which was prepared in the same manner of Example 1,except for depositing the silicon oxide gas barrier layer on PET filmwithout coating the first organic-inorganic hybrid buffer layer and thesecond organic-inorganic hybrid buffer layer.

Properties of the resultant plastic substrate were measured. The resultsare given in Table 6 below.

TABLE 6 Oxygen Water vapor Coefficient of transmission rate transmissionrate thermal expansion Transparency Haze (cc/m²/day/atm) (g/m²/day/atm)(ppm/K) (400 nm) (%) Comparative 1.1 2.0 22.1 >85% <0.3 Example 3

As seen in Table 6, the plastic substrate prepared in ComparativeExample 3 showed oxygen transmission rate of 1.1 and water vaportransmission rate of 2.0. This value was decreased more than PET film,relatively, but it shows still high value. In addition, It also showed alarge coefficient of thermal expansion, which is comparable to 22.4, orthe coefficient of thermal expansion of the PET substrate itself. Thus,in the case of Comparative Example 3, it is not a suitable substrate fora device.

Comparative Example 4

A plastic substrate shown in FIG. 6 was prepared by depositing thesilicon oxide gas barrier layer only on PET film.

Properties of the resultant plastic substrate were measured. The resultsare given in Table 7 below.

TABLE 7 Oxygen Water vapor Coefficient of transmission rate transmissionrate thermal expansion Transparency Haze (cc/m²/day/atm) (g/m²/day/atm)(ppm/K) (400 nm) (%) Comparative 3.1 3.0 22.0 >85% <0.3 Example 4

As seen in Table 7, the plastic substrate prepared in ComparativeExample 3 showed oxygen transmission rate of 3.1 and water vaportransmission rate of 3.0. This value was decreased more than PET film,relatively, but it shows still high value. In addition, it also showed alarge coefficient of thermal expansion, which is comparable to 22.4, orthe coefficient of thermal expansion of the PET substrate itself. Thus,in the case of Comparative Example 4, it is not a suitable substrate fora device.

Comparative Example 5

The buffer composition solution used in Example 1 was bar coated on oneside of a PET film to a thickness of 2.5 microns. Crosslinking anddeposition of a silicon oxide film having a thickness of about 100 nmwere performed as in Example 1 to form a gas barrier layer. Buffer layercoating, crosslinking, and silicon oxide film deposition were repeatedtwo more times. On the outermost silicon oxide film, another bufferlayer was coated to a thickness of about 3 microns. After removing theremaining solvent at 50° C. for 3 minutes, crosslinking was performed at125° C. for 1 hour to prepare a plastic substrate having non-symmetricalstacked only one side (FIG. 7). The resultant substrate measured 12cm×12 cm. When it was placed on a flat surface, it was bent upward, sothat the center region was spaced about 3 cm from the surface. Propertymeasurement results are given in Table 4 below. While oxygen and watervapor transmission rate was superior, the coefficient of thermalexpansion was not improved. Thus, in the case of Comparative Example 5,it is not a suitable substrate for a device.

TABLE 8 Oxygen Water vapor Coefficient of transmission rate transmissionrate thermal expansion Transparency Haze (cc/m²/day/atm) (g/m²/day/atm)(ppm/K) (400 nm) (%) Comparative <0.05 <0.005 22.2 >85% <0.3 Example 2

Comparative Example 6

The PET film used in Example 1 was dipped in a solution containing 0.3parts by weight of a polyfunctional methacrylate photoinitiator. Dipcoating was performed by raising the film at a rate of 10 cm/min. Then,UV curing was performed to form organic crosslinked coating layers onboth sides of the film. After UV curing, thickness of the crosslinkedcoating layers 140 a, 140 b measured with an alpha stepper was 3microns. A silicon oxide film having a thickness of 100 nm was depositedon the organic crosslinked coating layers in the same manner ofExample 1. Then, more organic crosslinked coating layers 142 a, 142 bwhere a plastic substrate prepared of FIG. 8 by coating on the siliconoxide barrier layers to a thickness of 3 microns to prepare a plasticsubstrate were produced. Property measurement results of the substrateare given in Table 9 below.

TABLE 9 Oxygen Water vapor Coefficient of transmission rate transmissionrate thermal expansion Transparency Haze (cc/m²/day/atm) (g/m²/day/atm)(ppm/K) (400 nm) (%) Comparative 0.08 0.01 22.3 >85% <0.3 Example 3

As seen in Table 9, although oxygen and water vapor transmission ratedecreased significantly compared with the PET substrate, the coefficientof linear expansion did not decrease.

As apparent from the above description, the plastic substrate of thepresent invention has a small coefficient of linear expansion, superiorgas barrier properties and excellent dimensional stability. Thus, it canreplace the glass substrate used for display devices. Also, it can beutilized for packaging and container materials in applications requiringsuperior gas barrier properties.

While the present invention has been described in detail with referenceto the preferred embodiments, those skilled in the art will appreciatethat various modifications and substitutions can be made thereto withoutdeparting from the spirit and scope of the present invention as setforth in the appended claims.

1. A plastic substrate having a multi-layer structure, comprising:plastic films attached to each other, and a first buffering layer of anorganic-inorganic hybrid, a layer of gas barrier, and a second bufferinglayer of an organic-inorganic hybrid which are stacked on both sides ofthe plastic films in an orderly manner, each layer forming a symmetricalarrangement centering around the plastic films, wherein each of thefirst organic-inorganic hybrid buffer layer and the secondorganic-inorganic hybrid buffer layer is prepared from partialhydrolysis of a buffer composition comprising 20-99.99 wt % of at leastone organic silane selected from the group consisting of the compoundsrepresented by Chemical Formula 1 below and 0.01-80 wt % of at least onemetal alkoxide selected from the group consisting of the compoundsrepresented by Chemical Formula 2:(R¹)_(m)—Si—X₍₄₋ m)  (1) where X, which may be identical or different,is hydrogen, halogen, C₁₋₁₂ alkoxy, acyloxy, alkycarbonyl,alkoxycarbonyl, or —N(R²)₂ (where R² is H or C₁₋₁₂ alkyl); R¹, which maybe identical or different, is C₁₋₁₂ alkyl, alkenyl, alkynyl, aryl,arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkynyl,alkynylaryl, halogen, substituted amino, amide, aldehyde, keto,alkylcarbonyl, carboxy, mercapto, cyano, hydroxy, C₁₋₁₂ alkoxy, C₁₋₁₂alkoxycarbonyl, sulfonate, phosphate, acryloxy, methacryloxy, epoxy, orvinyl; oxygen or —NR² (where R² is H or C₁₋₁₂ alkyl) may be insertedbetween R¹ and Si to give —(R¹)_(m)—O—Si—X_((4-m)) or(R¹)_(m)—NR²—Si—X_((4-m); and) m is an integer of 1-3; andM-(R³)z  (2) where M is a metal selected from the group consisting ofaluminum, zirconium, and titanium; R³, which may be identical ordifferent, is halogen, C₁₋₁₂ alkyl, alkoxy, acyloxy, or hydroxy; and Zis an integer of 3 or
 4. 2. The plastic substrate of claim 1, whereinthe plastic film is made of at least one selected from the groupconsisting of homopolymer, at least one polymer blend, and a polymercomposite material including organic or inorganic additives.
 3. Theplastic substrate of claim 2, wherein the polymer composite materialincluding inorganic additives is a polymer-clay nanocomposite in whichnano materials are dispersed in a polymer matrix.
 4. The plasticsubstrate of claim 1, wherein the gas barrier layer is made of at leastone inorganic material selected from the group consisting of SiO_(x)(where x is an integer of 1-4), SiO_(x)N_(y) (where each of x and y isan integer of 1-3), Al₂O₃, and ITO.
 5. The plastic substrate of claim 1,wherein the gas barrier layer has a thickness of 5-1,000 nm.
 6. Theplastic substrate of claim 1, wherein the buffer composition furthercomprises at least one filler selected from the group consisting ofmetal, glass powder, diamond powder, silicon oxide, clay, calciumphosphate, magnesium phosphate, barium sulfate, aluminum fluoride,calcium silicate, magnesium silicate, barium silicate, barium carbonate,barium hydroxide, and aluminum silicate; a solvent; and a polymerizationcatalyst.
 7. The plastic substrate of claim 1, wherein each of the firstorganic-inorganic hybrid buffer layer and the second organic-inorganichybrid buffer layer has a thickness of 0.5-20 microns (μm).
 8. A displaydevice comprising a plastic substrate, the plastic substrate having amulti-layer structure including: plastic films attached to each other,and a first buffering layer of an organic-inorganic hybrid, a layer ofgas barrier, and a second buffering layer of an organic-inorganic hybridwhich are stacked on both sides of the plastic films in an orderlymanner, each layer forming a symmetrical arrangement centering aroundthe plastic films.
 9. The display device of claim 8, wherein the plasticsubstrate has a water vapor transmission rate of 0.005 g/m²/day orlower.
 10. The display device of claim 8, wherein the plastic film ismade of at least one selected from the group consisting of homopolymer,at least one polymer blend, and a polymer composite material includingorganic or inorganic additives.
 11. The display device of claim 8,wherein the polymer composite material including inorganic additives isa polymer-clay nanocomposite in which nano materials are dispersed in apolymer matrix.
 12. The display device of claim 8, wherein each of thefirst organic-inorganic hybrid buffer layer and the secondorganic-inorganic hybrid buffer layer is prepared from partialhydrolysis of a buffer composition comprising 20-99.99 wt % of at leastone organic silane selected from the group consisting of the compoundsrepresented by Chemical Formula 1 below and 0.01-80 wt % of at least onemetal alkoxide selected from the group consisting of the compoundsrepresented by Chemical Formula 2:(R¹)_(m)—Si—X_((4-m))  (1) where X, which may be identical or different,is hydrogen, halogen, C₁₋₁₂ alkoxy, acyloxy, alkycarbonyl,alkoxycarbonyl, or —N(R²)₂ (where R² is H or C₁₋₁₂ alkyl); R¹, which maybe identical or different, is C₁₋₁₂ alkyl, alkenyl, alkynyl, aryl,arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkynyl,alkynylaryl, halogen, substituted amino, amide, aldehyde, keto,alkylcarbonyl, carboxy, mercapto, cyano, hydroxy, C₁₋₁₂ alkoxy, C₁₋₁₂alkoxycarbonyl, sulfonate, phosphate, acryloxy, methacryloxy, epoxy, orvinyl; oxygen or —NR² (where R² is H or C₁₋₁₂ alkyl) may be insertedbetween R¹ and Si to give —(R¹)_(m)—O—Si—X_((4-m)) or(R¹)_(m)—NR²—Si—X_((4-m)); and m is an integer of 1-3; andM-(R³)z  (2) where M is a metal selected from the group consisting ofaluminum, zirconium, and titanium; R³, which may be identical ordifferent, is halogen, C₁₋₁₂ alkyl, alkoxy, acyloxy, or hydroxy; and Zis an integer of 3 or
 4. 13. The display device of claim 12, wherein thebuffer composition further comprises at least one filler selected fromthe group consisting of metal, glass powder, diamond powder, siliconoxide, clay, calcium phosphate, magnesium phosphate, barium sulfate,aluminum fluoride, calcium silicate, magnesium silicate, bariumsilicate, barium carbonate, barium hydroxide, and aluminum silicate; asolvent; and a polymerization catalyst.
 14. The display device of claim8, wherein the gas barrier layer is made of at least one inorganicmaterial selected from the group consisting of SiO_(x) (where x is aninteger of 1-4), SiO_(x)N_(y) (where each of x and y is an integer of1-3), Al₂O₃, and ITO.
 15. The display device of claim 8, wherein the gasbarrier layer has a thickness of 5-1,000 nm.
 16. The display device ofclaim 8, wherein each of the first organic-inorganic hybrid buffer layerand the second organic-inorganic hybrid buffer layer has a thickness of0.5-20 microns (μm).